Photographic elements having gelatinous coating compositions containing amphoteric surface active agents



United States Patent 3,441,413 PHOTOGRAPHIC ELEMENTS HAVING GELATI- NOUS COATING COMPOSITIONS CONTAINING AMPHOTERIC SURFACE ACTIVE AGENTS Fumihiko Nishio and Kameji Nagao, Kanagawa-ken, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa-ken, Japan, a corporation of Japan No Drawing. Filed July 2, 1965, Ser. No. 469,319 Claims priority, application Japan, July 7, 1964, 39/38,556 Int. Cl. G03c 1/02 US. CI. 9694 12 Claims This invention relates to an improved photographic element adapted for photographic purposes, which contains as a coating aid an amphoteric surface active agent having the following general formula:

wherein R is an alkyl group having 8 to 18 carbon atoms, 12 and q are each integers greater than zero, p-i-q is an integer from 2 to 18.

In general, as a support for a photographic product, there have been known nitrocellulose, triacetyl cellulose, polycarbonate, polyester, other synthetized macromolecular materials, glass plate, papers, etc. On such a support is coated a silver halide photographic emulsion layer directly or through a substratum. The substratum contributes to adhere strongly the photographic emulsion layer onto the support. Further, a photographic product is usually coated with a thin gelatin layer on the photographic silver halide emulsion layer in order to prevent sticking of the emulsion layer to the surfaces of similar materials or different materials and to prevent the formation of scratches by pressing. Therefore, since a photographic product generally consists of many layers as mentioned above, a photographic silver halide emulsion layer or a protective layer cannot be uniformly coated Without the aid of a surface active agent for spreading uniformly the coating gelatinous solution and improving the wetting property of the coating solution. The use of such a surface active agent also prevents the formation of foams and repellencies.

As one embodiment of applying a gelatinous solution on a support in multilayers, there is the production of a color film wherein three different photographic silver halide emulsions are coated continuously on a support in three layers. The coating problems in the case where a gelatin layer or other colloid layer is coated on a gelatinous layer are completely different from the case where a gelatinous layer is directly coated on a support. In particular, this is true in the case where the emulsion 3,441,413 Patented Apr. 29, 1969 while set and in a chilled set condition to to be overcoated with another emulsion or with a protective gelatin coating.

That is, in this case, the surface of a support must be uniformly wetted with a coating solution, and the surface of the layer formed from the coating solution by setting or drying, must be uniformly wetted with an overcoating solution.

Moreover, it is desirable that a dried surface is easily wetted with an aqueous solution for that the photographic film or paper is easily wetted with a treating solution in a photographic processing such as development and that there is no unevenness and no foaming.

Beside the above-mentioned unevenness in coating caused by the lack of good wetting property, there occurs spot-like unevenness caused by hydrophobic materials contained in gelatin such as a small amount of fat. In this case, the surroundings of the hydrophobic materials are reduced in the thickness of coating to form spots and a phenomenon called repellence or comet occurs. Commercially available gelatin generally contains a small amount of fat inevitably and hence in order to prevent the formation of the comet, etc., which is considered to be caused by the presence of the fat, the addition of a surface active agent is necessary.

Hitherto, saponin has been broadly used in the photographic industry as a spreading agent, and it can be further utilized in a larger range than other various surface active agents. However, saponin is a naturally occurring substance and may show decided variations in quality from batch to batch.

For this reason, as the surface active agents for photographic industry, synthetic materials have recently been used. There are many patents about such surface active agents in which, however, besides the use for the spreading agent, many merits by the surface active agents are described, such as, antistatic effect, improvement of the solubility of couplers, improvement of the permeability of treating solutions, reduction of troubles caused by water drops, vanishing of bubbles in the case where a gelatin sol is applied on a chilling-set emulsion layer, promotion of increase in photographic sensitivity by development, prevention of a support from being contaminated by halation-preventing dyes, and the like. However, almost all of these synthetic surface active agents are very peculiar to these effects and hence in some cases, they give good effects to a specific photographic emulsion and a gelatin composition but in other case, they are completely useless to other compositions in the improvement of wetting property and the prevention of the formation of comets. Therefore, the uses of almost all synthetic surface active agents are limited. Then, the utilization of many different types of surface active agents to photographic industry have been proposed. Further, as the problems about conventional synthetic surface active agents there are recognized that the wettability of a coating solution to a substratum or an already coated emulsion layer does not always coincide with the wettability of another coating solution or a treating solution to coating formed by applying the former coating solution on a support, and, on the contrary, in the case of using an easily coatable coating solution, it is usually difficult to coat on thus coated layer with another coating solution. Similarly, about the formation of comets and wetting ability of coating, the case profitable to one is usually unprofitable to another.

Further, it has been already known that a compound containing polyalkylene oxide has generally an effect for increasing the photographic sensitivity of a silver halide photographic product but in this invention it has been confirmed that only the coating property for a photographic product can be improved without giving influences on photographic properties, such as, photographic sensitivity, gamma, and fog.

Therefore, an object of this invention is to coat a photographic emulsion or a gelatin composition on a support without the formation of comets and the like, said photo- The following examples will serve to understand the invention in detail while the invention is not by any means limited to them.

EXAMPLE 1 graphic emulsion or the gelatin composition being, after 5 A gelatinPQs Silver chlorqbromide em111i011 Was P it is formed into a layer on the support, easily wetted by pared contalmng 8.0% gelat n and 4.5% silver salts. To a treating solution. one kilogram of th1s emulsion was added an aqueous Another object of this invention is to coat a photosolution having the following composition.

Amount Additive 2-) Sample No.:

1 Nothing (Control) 2 Compound 1 20 3 do 50 4 lo 100 5 Sodium dodecylbenzene sulfonate 100 6 Polyoxyethylenenonylphenyl ether (n=) 100 7 Compound 1 and sodium dodecylbenzene sulfonate- (CH2CH2O)DH R-fvornomonn wherein R represents an alkyl group having 8 to 18 carbon atoms, 12 and q are integers greater than zero and p-i-q is an integer of from 2 to 18.

As examples of such compounds, there are:

Compound 1 CHzCHeOH OmmG-ornomon Compound 2 onzomonn CrzHniI-(CHzCHzOhH Compound 3 (CH2CH2O)DH onH2g1 oHzoH2o ,H

Compound 4 cnzonm n 1s a7 (C 2CH2O) H Compound 5 (CH:CH2O),,H ClzHfiKI-(CHgOIIzOMH CHzC O O- The above-mentioned compounds may be obtained by reacting an alkyl amine with ethylene oxide and then reacting the product with monochloroacetic acid.

These surface active agents may be added in a photographic coating solution in an amount of about 0.05-50 g., preferably 0.35 g. per 1 kg. of dried gelatin. These surface active agents may be used individually or as a mixture thereof, or may be used with other surface active agent.

(p-i q Thus prepared emulsion was coated on a subcoated film base by passing the film base under a coating roller so that the subcoated surface of the film base was dipped in the emulsion. The emulsion Was immediately setted by chilled air but was not dried, and one kilogram gelatinous solution containing 20 g. of gelatin and 150 mg. of saponin was overcoated on the emulsion layer immediately without drying the emulsion as in the case of coating the emulsion.

In this case, the coating procedure of the protective coating solution was conducted by changing the passing speed of the film base that had been coated with the gelatinous silver halide emulsion to determine the maximum speed at which the protective coating solution was coated uniformly on the surface of the emulsion layer, which was defined as the limiting speed (the higher the limiting speed, the more profitable for the production). After the end of coating and drying, thus prepared film was examined about the number of portions where the coating of emulsion became uneven and the thickness of coating was thinned spot-likely, which are generally called comets (of course, the less the comet number, the better). The results were as follows.

Limiting speed (m. min.)

0 Above 23 As shown in the above table, by the process of this invention (sample Nos. 2, 3, 4 and 7), the conditions of the high limiting speed and less comet number were obtained, while by the addition of a typical anion surface active agent, sodium dodecylbenzene sulfonate (sample No. 5), the limiting speed at which the comet number was less was low. Further, by the addition of a typical nonionic surface active agent, polyoxyethylene nonylphenyl ether (sample No. 6), the limiting speed was increased but the comet number was also increased. Moreover, in an embodiment of this invention, wherein Compound 1 in this invention was used with sodium dodecylbenzene sulfonate (sample No. 7), the conditions of the high limiting speed and less comet number were obtained. When the photographic products that had been prepared by the process of this invention were developed with a commercially available metol-hydroquinone developer, no bad influences were observed on the photographic properties, such as, photographic sensitivity, gamma, and fog.

EXAMPLE 2 A photographic emulsion containing g. of gelatin, 62 g. of silver iodobromide, mg. of saponin, and

Comet No..sq.m.

5 6 60 mg. of polyoxyethylene nonylphenyl ether (rt-=15) obtained intermediate film product was, without being per 1 kg. of emulsion was coated on a film base as in dried, immediately coated with a gelatin solution con- Example 1. After drying, a protective coating solution taining 20 g. of gelatin, 200 mg. of dodecylbenzene sulcontaining 1.5 g. of gelatin per 1 kg. and the following fonic acid, and 800 mg. of saponin per 1 kg. as in the surface active agent was applied on it. case of coating the emulsion.

Additives Amount 1 Limiting speed Sample No.: Additive (m./min.)

1 Nothing (control) 2- Compound 2. 20 Sample 3.. do 50 10 No.: 4 do 100 1 Nothing (control) 0 Sulfuric acid ester of lauryl alcohol 100 2 Compound 3 l5 6 Sodium dodecylbenzene sulfonate 100 3 Saponin 3 7 Polyoxyethylene nonylphenyl ether..-" 100 4 Sodium dodecylbenzene sulionate 3 5 Polyoxyethylene nonylphenyl ether (n=10) 0 mgkg. of gelatin solution.

Thus coated and dried samples were examined about Thus, in the case of this invention (sample No. 2),

the comet number. Further, a developing solution was the limiting speed was extremely superior to the cases of dropped onto the sample that has been placed horizonusing other known typical surface active agents (3, 4 and tally and the contact angle was measured by a micro- 5). Further, the color tone, gradation, and photographic scope having a low magnifying power. If the contact sensitivity of the photographic product were not reduced angle is large, the film is not easily wetted when it is by color development. dipped into the developer and the large contact ange causes attaching of foams and the formation of uneven- EXAMPLE 4 ness. Therefore, the contact angle is preferably small. After adding an orthochromatic sensitizer, a stabilizer, The measured comet number and contact angle were and a hardening agent into 100 Parts of a Silver chloroh w inth follo in t m bromide gelatin emulsion prepared by a conventional method, the emulsion was added with 5 parts of a 5% Contact angle, Comet number aqueous solution of l(4'-phenoxy 3 sulfophenyl)-3- heptadecyl-S-pyrazolone and then 2 cc. of a 2% aqueous 47 Above 20 solution of the compound shown in the following table. g g The emulsion was applied on a subcoated film base fol- 23 0 lowed by drying. On thus formed emulsion layer was 2% 3 applied a 2% gelatin solution containing a hardening 3o 15 agent and 1 -g./liter of saponin with a coating speed of 5 mjmin.

Additive Comet No./sq. m.

Sample No.:

1 Nothing (control) Above 20 2---- Compound4 0 3.. Sodium dodecylbenzene sulionate 5 4 Polyoxyethylene nonylphenyl ether (n=10) Above 20 5. Compound 4 and Sodium dodecylbenzene sulfonate--. 0

As clear from the above table, in the case of this As clear from the above table, the case of using the invention, the contact angle was small and the1 comet process of this invention showed no comet number. number was small. In the cases of using a typica anion surface active agent, sulfuric acid ester of lauryl alco- EXAMPLE 5 hol (sample No. 5) and sodium dodecylbenzene sul- The process ofExample 4 was carried out in the same fonate (sample No. 6), the comet number was reduced manner except using Compound 5 instead of Compound 4 but the contact angle was increased and the surface of and almost same results were obtained. the film became Water-repellent. Further, in the case of What is claimed is: using a typical nonionic surface active agent, polyoxy- 1. A photographic element comprising a support havethylene nonylphenyl ether -(n=10) (sample No. 7), ing thereon at least one light-sensitive silver halide gelait was impossible to remove comets completely. tinous emulsion layer, said layer containing a compound When the photographic product prepared by the prochaving the following general formula ess of this invention was developed by a commercially available phenidonehydroquinone developer, no bad in- (CHZCHzOMH fluences were observed on the photographic properties, R-N(CH2CH2O) H such as, photographic sensitivity, gamma, and fog. 0112000- EXAMPLE 3 wherein R represents an alkyl group havlng from 8 to 18 An emu.ls.lon was prgiared by addmg p f carbon atoms, p and q are each integers greater than color sensitizer, a stabllizer and a hardening agent into Zero and 12+ q is an integer from 2 to 100 parts of a silver iodobromrde gelatin emulslon that 2. The photographic element according to claim 1 has q g gg g i gi g g f; i i ggii i g i 5 wherein said compound is shown by the following forsensi izer an a g mula a conventional method. Apart from this, a solution of 10 parts l-hydroxy-N-dodecyl-Z-naphthamide in 10 parts of dibutyl phthalate was dispersed in 100 parts of a 10% CHZCHZOH gelatin solution using sodium butylnaphthalene sulfo- OBHU1ZCH2CH2OH nate. Into 100 parts of the above-prepared silver halide CH0 photographic emulsion was added 10 parts of thus prepared dispersion containing the coupler. The emulsion was further added with 2 cc. of a 2% methanol solution 3. The photographic element according to claim 1 of the compound shown in the following table and apwherein said compound is shown by the following forplied on a subcoated film base as in Example 1. Thus mula wherein p and q are each integers greater than zero and 4. The photographic element according to claim 1 wherein said compound is shown by the following formula (CH2CH20) H onngriromonzonn CHzCOO wherein p and q are each integers greater than zero and I 5. The photographic element according to claim 1 wherein said compound is shown by the following formula (OHzOHzOhH CmHwr I- omomonrr CHzCOO- wherein p and q are each integers greater than zero and 6. The photographic element according to claim 1 wherein said compound is shown by the following formula orncnzm n omnga lomomonrr CHzC 0- wherein p and q are each integers greater than zero and P+q= 7. A photographic element comprising a support having thereon at least one light-sensitive silver halide gelatinous emulsion and at least one subsidiary layer, at least one of said layers containing a compound having the following general formula onicnzo n RI I(CHzOHzO) H wherein R represents an alkyl group having from 8 to 18 carbon atoms, p and q are each integers greater than zero and p-l-q is an integer from 2 to 18.

8. The photographic element according to claim 6 wherein said compound is shown by the following formula 9. The photographic element according to claim 6 wherein said compound is shown by the following formula (CH2CH2O)DH ournsfiomonzm n ornooowhereiriop and q are each integers greater than zero and P+q= 10. The photographic element according to claim 6 wherein said compound is shown by the following formula (CHzCHzOhH CuHzglG-(CHzCHzOMH CHzCOO wherein p and q are each integers greater than Zero and P+q= 12. The photographic element according to claim 6 wherein said compound is shown by the following formula (oH2oH2o ,,H C12Hz5I I(CH2CH2O) H omooowherein p and q are each integers greater than zero and References Cited UNITED STATES PATENTS 2,271,623 2/1942 Carroll 96104 3,017,271 1/1962 Piper 96107 3,113,026 12/1963 Sprung 96-107 0 J. TRAVIS BROWN, Primary Examiner. 

